Method of making polyepoxide modified oxyalkylation derivatives, said derivatives obtained in turn by oxyalkylation of phenol-aldehyde resins and product resulting therefrom



Unimd aes Pa ent Melvin De Groote, St. Louis, and Kwan-Ting Shen,

Brentwood, Mo., assignors to Petrolite Corporation,

Wilmington, DeL, a corporation of Delaware No Drawing. Originalapplication November 19, 1953, Serial No. 393,222, new Patent No.2,792,355, dated May. 14, 1957. Divided and this application January 22,1957, Serial No. 635,150

3 Claims. (Cl. 260-43) The present application is a continuation-impartof our co-pending applications, Serial Nos. 343,804, filed March 20,1953, now abandoned, and Serial No. 349,972, filed April 20, 1953, nowU. S. Patent No. 2,792,353, dated May 14, 1957, and a division of ourcopending application Serial No. 393,222, filed November 19, 1953, nowU. S. Patent No. 2,792,355, dated May 14, 1957.

The first of said copending applications relates to processes forbreaking petroleum emulsions of the water-in-oil type employing ademulsifier including the reaction prodnets of (A) certain oxyalkylatedphenol-aldehyde resins, therein described in detail, and (B) certainphenolic polyepoxides and cogcnerically associated compounds formed intheir preparation, also therein described in detail, the ratio ofreactant (A) to reactant (B) being in the proportion of two moles of (A)to one mole of (B).

The second of the aforementioned co-pending applications is comparableto the above application, Serial No. 343,804, except that thepolyepoxide employed is a nonaryl hydrophile polyepoxide which istherein described in detail.

Note that in both patent applications the molal ratio of oxyalkylatedresin to polyepoxide is 2 to 1'.

In our 2 copending applications, Serial Nos. 393,221, now U. S. PatentNo. 2,819,212, dated January 7, 1958, and 393,223, now U. S. Patent No.2,792,356, dated May 14, 1957, the same situation applies except thatthe molar ratio is 4 m3 instead of 2 to 1. Co-pending application,Serial No. 393,221 employs the same type of polyepoxide as in Serial No,343,804. Likewise, co-pending application, Serial No. 393,223 employsthe same type of epoxide as co-pending application, Serial No. 349,972.

In the present application the molal ratio again is 4 to 3 and not 2 to1 and involves both types of polyepoxides. Stated another way, thehydrophobe polyepoxide described in Serial No. 343,804 is employed firstin a 2 to 1 ratio, and then 2 moles of this larger molecule are unitedby one mole of the hydrophile polyepoxide described in Serial No.349,972. Thus, it is obvious thatthe present application employs theproducts described in Serial No. 343,804 as an intermediate. For thisreason much of the text is identical with that found in Serial No.343,804 but that part of the text which describes the hydrophilepolyepoxide in Serial No. 349,972 also appears in the presentdescription.

Thus the present invention relates to new chemical products or compoundsuseful as demulsifying agents in processes or procedures particularlyadapted for preventing, breaking or resolving emulsions of thewater-in-oil type and particularly petroleum emulsions. The new productsare the reaction products of (A) certain oxyalkylated phenol-aldehyderesins, hereinafter described in detail, and (B) certain phenolicpolyepoxides and cogenerica'lly associated compounds formed in theirprepara tion, hereinafter described in detail, further reacted with2,839,489 Patented June 17, 1958 (C) certain non-aryl hydrophilepolyepoxides, also hereinafter described in detail. The reactants (A)and (B) are reacted in the molar proportion of 2 ml respectively to forman intermediate (ABA) and this intermediate is reacted with (C) in themolar proportion of 2 to 1 respectively to produce the final reactionproduct (ABACABA). 1

These products are obtained from certain hydroxylated heat-stableresins, which, since they are heatstable, are also susceptible toreaction in various ways to yield products other than oxyalkylationproducts, such as imine de rivatives. Such imine derivatives may beobtained, for example, by subjecting the resins to reaction withethylene imine, propylene imine, or similar imines rather than reactionwith ethylene oxide, propylene oxide, etc; Comparable compounds areobtained by derivatives which, in addition to having the imine radical,have on ether linkage such as wherein R is a comparatively small alkylradical, such as methyl, ethyl, propyl, etc. In light of this fact, i.e., that the reaction products of the selected resins herein describedand the epoxides are apparently new per se and may be utilized in amanner other than specifically de scribed herein, it is obvious theyrepresent part of the instant invention. The resultarlts obtained byreaction between the resinous materials and the imine type reactantexemplify new compounds having properties usually found in cationicsurtace-active agents and can be used for the purposes for which thesematerials are commonly employed. The materials so obtained are stillsusceptible to oxyalkylation with an alkylene oxide, such as ethyleneoxide, propylene oxide, etc., and can be reacted with these oxides inthe same manner as herein described in connec tion with the resinousmaterials which have not been subjected to the intermediate reactionwith an imine.

Actually any reference in the claims or specification to the property ofbeing "oxyalkylation-susceptible might just as properly be characterizedas being imine-reactive or for that matter as oxyalkylation-susceptibleand iminereactive.

The products obtained by reaction between the oxyalkylated derivativesand the polyepoxides are obviously acylation-susceptible as well asbeing oxyalkylation-susceptible. For instance, they could be subjectedto reaction with alklene oxides different than those previouslydescribed as, for example, styrene oxide. These derivatives additionallymust have a number of aliphatic hydroxyl groups. Such aliphatic hydroxylgroups as dilierentiated from phenolic hydroxyl groups present in one ofthe initial reactants are particularly susceptible to acylation withvarious carboxylic and non-carboxylic acids. They may be reacted withdetergent-forming monocarboxy acids particularly higher fatty acids,which are saturated or unsaturated, as well as polycarboxy acids, suchas phthalic anhydride, maleic anhydride, etc. Similarly, they can bereacted with maleic acid or a fractional maleic acid ester, such asthermono-octyl ester of maleic acid, and the neutral ester obtained canbe reacted with sodiumv bisulfite so as to introduce a sulfonic group.

Not withstanding the fact that subsequent data will be presented inconsiderable detail, yet the description becomes somewhat involved andcertain facts should be kept in mind. The polyepoxides, and particularlythe diepoxides may have no connecting bridge between the phenolic nucleias in the case of a diphenyl derivative, or may have a variety ofconnecting bridges, i. e., divalent linking radicals. Our preference isthat either diphenyl compounds be employed or else compounds where thedivalent link is obtained by the removal of a carbonyl oxygen atom asderived from a ketone or aldehyde.

As far as the hydrophobe polyepoxides go and particularly the hydrophobediglycidyl ethers, used in the first stage or the preparation of theintermediate, if it were not for the expense involved in preparating andpurifying the monomer We would prefer it to any other form, i. e., inpreference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kinddescribed as first-stage reactants, for example, in U. S. Patent2,530,353, dated November 14, 1950. Said patent described compoundshaving the general formula Wherein R is an aliphatic hydrocarbon bridge,each n independently has one of the values 0 to 1, and X is an alkylradical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination withthe reactive oxyalkylated phenol-aldehyde resin are characterized by thefollowing formula and cogenerically associated compounds formed in theirpreparation:

H: H H: H 531 Hg in which R represents a divalent radical selected fromthe class of ketone residues formed by the elimination of the ketonicoxygen atom and aldehyde residues obtained by the elimination of thealdehydic oxygen atom, the divalent radical the divalent 0 II C radical,the divalent sulfone radical, and the divalent monosulfide radical S,the divalent radical and the divalent disulfide radical SS; and R 0 isthe divalent radical obtained by the elimination of a hydroxyl hydrogenatom and a nuclear hydrogen atom from the phenol in which R, R", and Rrepresent hydrogen and hydrocarbon substitutents of the aromaticnucleus, said substituent member having not over 18 carbon atoms; nrepresents an integer including zero and l, and )1 represents a wholenumber not greater than 3. The above mentioned compounds and thoseassociated compounds formed in their preparation are thermoplastic andorganic solvent-soluble. Reference to being thermoplastic characterizesproducts as being liquids at ordinary temperature or readily convertibleto liquids by merely heating below the point of pyrolysis and thusdifferentiates them from infusible resins. Reference to being soluble inan organic solvent means any of the usual organic solvents, such asalcohols, ketones, esters, ethers, mixed solvents, etc. Reference tosolubility is merely to differentiate from a reactant which is notsoluble and might be not only insoluble but also infusible. Furthermore,solubility is a factor insofar that it is sometimes desirable to dilutethe compound containing the epoxy rings before reacting with the resin.In such instances, of course, the solvent selected would have to be onewhich is not susceptible to oxyalkylation, as, for example, kerosene,benzene, toluene, dioxane, various ketones, chlorinated solvents,dibutyl ether, dihexyl ether, ethyleneglycol diethylether,diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The1,2-epoxy ring is sometimes referred to as the oxirane ring todistinguish it from other epoxy rings. Hereinafter, the word epoxy,unless indicated otherwise, will be used to mean the oxirane ring, i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or moreoxirane rings they will be referred to as polyepoxides. They usuallyrepresent, of course, 1,2- epoxide rings or oxirane rings in thealpha-omega position. This is a departure, of course, from thestandpoint of a strictly formal nomenclature as in the example of thesimplest diepoxide which contains at least 4 carbon atoms and isformally described as l,2-epoxy-3,4-epoxybutane 1,2-3,4-diepoxybutane)It well may be that even though the previously suggested formularepresents the principal component, or components, of the result orreaction product described in the previous test, it may be important tonote that somewhat similar compounds, generally of much higher molecularweight, have been described as complex resinous epoxides which arepoiyether derivatives of polyhydric phenols containing an average ofmore than one epoxide group per molecule and free from functional groupsother than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295,dated January 10, 1950, to Greenlee. The compounds here included arelimited to the monomers or the low molal members of such series andgenerally contain two epoxide rings per molecule and may be entirelyfree from a hydroxyl group. This is important because the instantinvention is directed towards products which are not resins and havecertain solubility characteristics not inherent in resins. Note, forexample, that said U. S. Patent No. 2,494,295 describes products whereinthe epoxide derivative can combine with a sulfonamide resin. Theintention in said U. S. Patent 2,494,295, of course, is to obtainultimately a suitable resinous product having the characteristics of acomparatively insoluble resin. The intent in the present instance in acomparable example would be to use a sulfonamide (not a sulfonamideresin) and obtain a material which does not have the characteristics ofan ordinary varnish resin or the like, i. e., is permanently soluble,and stays soluble generally as a liquid of ordinary viscosity, or as athick viscous liquid and maybe a thermoplastic solid, and additionallyeven may be water-soluble.

Having obtained a reactant having generally 2 epoxy rings as depicted inthe last formula preceding, or low molal polymers thereof, it becomesobvious the reaction can take place with any one of a number ofoxyalkylated resins which are still oxyalkylation-susceptible. There isavailable considerable literature, particularly patent literaturedealing with oxyalkylated resins of the kind herein employed forreaction with the selected polyepoxides. These will be referred to ingreater detail. subsequently. For purpose of convenience, reference issimply made at the moment to the following patents: U. S. Patent Nos.2,499,365; 2,499,366; 2,499,367; 2,499,368; and 2,499,370, all datedMarch 7, 1950 to De Groote and Keiser.

To illustrate the products which represent the subject matter of thepresent invention reference will be made to a reaction involving a moleof the olyalkylating agent, i. e. the compound having two oxiraue ringsand oxyalkylated epoxypropane.

resins as described. Proceeding with the example previously described itis obvious the reaction ratio of two moles of the oxyalkylated resin toone mole of diepoxide gives a product which may be indicated as follows:

6 in-oil type, is characterized by the fact that a 50-50 solution inxylene, or its equivalent, when mixed with one to three volumes of waterand shaken will produce an emulsion.

(oxyalkylated resin) in which the various characters have their priorsignificance. However, molal ratios may be varied as noted subsequently.

Such products must be soluble in suitable solvents such as anon-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent,or for that matter, a mixture of the same with water. Needless to say,after the resin has been treated with a large amount of ethylene oxidethe products are water soluble and may be soluble in an acid solution.

The purpose in this instance is to difierentiate from insoluble resinousmaterials, particularly those resulting from gelation or cross-linking.Not only does this property serve to ditferentiate from instances Wherean insoluble material is desired, but also serves to emphasize the factthat in many instances the preferred compounds have distinctWater-solubility or at least distinct dispersibility in water. Forinstance, the products freed from any solvent can be shaken with five totwenty times their weight of distilled water at ordinary temperature andare at least self-dispersing, and in many instances watersoluble, infact colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of areactant having both a nitrogen group and a 1,2-epoxy group, such as3-dialkylamino- See .U. S. Patent No. 2,520,093, dated August 22, 1950,to Gross.

As far as the use of the herein described products goes for the purposeof resolving petroleum emulsions of the water-in-oil type, and also forthat matter for numerous other purposes where surface-active materialsare effective, and particularly for those uses specified elsewhereherein, we prefer to employ oxyalkylated derivatives, which are obtainedby the use of monoepoxides, in such manner that the derivatives soobtained have sufficient hydrophile character to meet at least the testset forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to DeGroote, et al. In said patent such test for emulsification using awater-insoluble solvent, generally xylene, is described as an index ofsurface activity.

In the presentinstance the various oxyalkylated derivatives obtainedparticularly by use of ethylene oxide, propylene oxide, etc., may notnecessarily be xylenesoluble although they are xylene-soluble in a largenumber of instances. If such compounds are not xylene-soluble theobvious chemical equivalent, or equivalent chemical test, can be made bysimply using some suitable solvent, preferably a water-soluble solventsuch as ethylene glycol diethylether, or a low molal alcohol, or amixture to dissolve the appropriate product being examined and then mixwith the equal weight of xylene, followed by addition of Water. Suchtest obviously is the same for the reason that there will be two phaseson vigorous shaking and surface activity makes its presence manifest. Itis understood the reference in the hereto appended claims as to the useof Xylene in the emulsification test includes such obvious variant.

Reference is made again to U. S. Patent No. 2,499,368, dated March 7,1950, to De Groote and Keiser. Attention is directed to that part of thetext which appears in columns 28 and 29, lines 12 through 75, and lines1 through 21, respectively. Reference is made to this text with the sameforce and effect as if it were herein included. This, in essence, meansthat the preferred prodnot for resolution of petroleum emulsions of thewater- (oxyalkylated resin) For purpose of convenience what is saidhereinafter will be divided into ten parts with Part Three, in turn,being divided into three subdivisions;

Part 1 is concerned with our preference in regard to the hydrophobe typeof polyepoxide and particularly the hydrophobe type of diepoxidereactant, i. e., the one that enters into the formation of theintermediate ABA.

Part 2 is concerned with certain theoretical aspects of diepoxideprepared With the hydrophobe type, i. e., the one identified as Type B,preceding.

Part 3, Subdivision A, is concerned with the preparation of monomerichydrophobe type diepoxides, including Table I.

Part 3, Subdivision B, is concerned with the preparation of low molalhydrophobe type polymeric epoxides or mixtures containing low molalhydrophobe type polymeric epoxides as well as the monomer and includesTable II.

Part 3, Subdivision C, is concerned with miscellaneous phenolicreactants suitable for low molal hydrophobe type diepoxide preparation.

Part 4 is concerned withsuitable phenol-aldehyde resins to be employedfor reaction with the epoxides.

Part 5 is concerned with the oxyalkylation of the previously describedphenol-aldehyde resins.

Part 6 is concerned with the procedure involving preparation of anintermediate by reaction between 2 moles of the oxyalkylatedphenol-aldehyde: resin and one mole of the diglycidyl ether for example(identical with the products described in aforementioned copendingapplication, Serial No. 343,804) followed by a second step in which 2moles of these larger molecules are combined with use of a single moleof a diglycidyl ether or the like. This intermediate has been describedpreviously as ABA.

Part 7 is concerned with suitable hydrophile nonaryl polyepoxides andparticularly diepoxides employed as the reactant in uniting 2 moles ofthe intermediate ABA by means of a hydrophile epoxide and particularly ahydrophile diepoxide described as (C) to yield the final productdescribed as ABACABA.

Part 9 is concerned with the resolution of petroleum emulsions of thewater in-oil type by means of the previously described chemicalcompounds or reaction prodnets; and

Part 10 is concerned with uses for the products herein described, eitheras such or after modification, including uses in applications other thanthose involving resolution of petroleum emulsions of the water-in-oiltype.

.PAR 1 As will be pointed out subsequently, the preparation ofpolyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. if such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solventsoluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in which there are more than two epoxiclegroups per molecule. Thus, for practical purposes What is saidhereinafter is largely limited to polyepoxides in the form ofdiepoxides.

As has been pointed out previously one of the reactants employed is adiepoxide reactant. It is generally obtained from phenol(hydroxybenzene) or substituted phenol.

The ordinary or conventional manufacture of the epoxides I usuallyresults in the formation of a co-generic mixture as explainedsubsequently. Preparation of the monomer or separation of the monomerfrom the remaining mass of the cogeneric mixture is usually expensive.If monomers were available commercially at a low cost, or if they couldbe prepared without added expense for separation, our preference wouldbe to use the monomer. Certain monomers have been prepared and describedin the literature and will be referred to subsequently. However, from apractical standpoint one must weigh the advantage, if any, that themonomer has over other low molal polymers from a cost standpoint; thus,we have found that one might as well attempt to prepare a monomer andfully recognize that there may be present, and probably invariably arepresent, other low molal polymers in comparatively small amounts. Thus,the materials which are most apt to be used for practical reasons areeither monomers with some small amounts of polymers present or mixtureswhich have a substantial amount of polymers present. Indeed, the mixturecan be prepared free from monomers and still be satisfactory. Briefly,then, our preference is to use the monomer or the monomer with theminimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be directly united, or united through a variety ofdivalent radicals. Actually, it is our preference to use those which arecommercially available and for most practical purposes it meansinstances where the phenolic nuclei are ither united directly withoutany intervening linking radical, or else united by a ketone residue orformaldehyde residue. The com- "mercial bis-phenols available now in theopen market illustrate one class. The diphenyl derivatives illustrate asecond class, and the materials obtained by reacting substitutedmonofunctional phenols with an aldehyde illustrate the third class. Allthe various known classes may be used but our preference rests withthese classes due to their availability and ease of preparation, andalso due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way,as pointed out elsewhere, our preference is to produce them by means ofthe epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains onlya modest amount of polymers corresponds to the derivative of bis-phenolA. It can be used as such, or the monomer can be separated by an addedstep which involves additional expense. This compound of the followingstructure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of theother epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higherpolymers are satisfactory. The formula for this compound is Referencehas just been made to bis-phenol A and a suitable epoxide derivedtherefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2isomers being present. It is immaterial which one of these isomers isused and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, towit, Part 1, and in succeeding parts, the text is concerned almostentirely with epoxides in which there is no bridging radical or thebridging radical is derived from an aldehyde or a ketone. It would beimmaterial if the divalent linking radical would be derived from theother groups illustrated for the reason that nothing more than meresubstitution of one compound for the other would be required. Thus, whatis said hereinafter, although directed to one class or a few classes,applies with equal force and effect to the other classes of epoxidereactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reason that any time that alow-molal sulfurcontaining compound can react with epichlorohydrin theremay be formed a by-product in which the chlorine happened to beparticularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derivedby more than one-method as, for example, the use of epichlorohydrin orglycerol dichlorohydrin. A number of problems are involved in attemptingto produce these materials free from cogeneric materials of relatedcomposition. For a discussion of these difliculties, reference is madeto U. S. Patent No. 2,819,212, beginning at column 7, line 21.

PART 3 Subdivision A The preparations of the diepoxy derivatives of thediphenols, which are sometimes referred to as diglycidyl ethers, havebeen described in a number of patents. For convenience, reference willbe made to two only, to wit, aforementioned U. S. Patent 2,506,486, andaforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides,

' or diglycidyl ethers as they are sometimes termed, are

included for purpose of illustration. These particular compounds aredescribed in the two patents just mentioned.

TABLE I Ex- Patent ample Diphenol Diglycidyl ether refernumber enceCH2(C6H4OH)2 Di(epoxypropoxyphenyl)methane 2, 506, 486 CH3OH(G H OH)Di(ep0xypr0poxyphenyl)mothylmethane 2, 6, 486 (CHmO (G H OH)2Di(epoxypropoxyphenyl)dimethylmethana- 2, 506, 486 021150 (CH (O H1,ODi(epoxypropoxyphenyl)ethylmethylm ethan 2, 506, 486 (0971 920 (O H OH)z Di(epcxypropoxyphenyl)dieth ylm ethane..." 2, 506, 486 OH O(O;,H(0|3H4OH)2 Di(epoxypropoxyphenyl)Inethylpr0pylmethane 2, 506, 486 (EH30(CfiHs) (CGH4OII)2 Dl (cpoxypropoxyphenyhm ethylphcnylm ethane. 2, 506,486 011150 (Cal-I (G H OHl 2... Dl(epoxypropoxyphenyl)ethylpnenylmethane2, 506, 486 O3H C 0011 (0 11 011) Di(epoxypropoxyphenyl)propylphenylmethane- 2, 506, 486 Di(epoxypropoxyphonyl)butylplxenylmethane. 2, 506,486 Di(epoxyprop0xypnenyl)tolylrnethane 2, 506, 486 (OH3CtH4)C(OH3) (CILOLE D1(epoxypropoxyphenybtolylmethylmethane 2, 506, 486 DihydroxydiphenyL 4,4-bis(2,3-ep0xypropoxy)diphenyl 2, 530, 353 (CH3) 0(04115.05113011) 2. 2,2-bis(4-(2,3-epoxypr0poxy)2tert1arybutyl phenyl)propane 2, 530, 353

Subdivision B As to the preparation of low-molal polymeric epoxides ormixtures reference is made to numerous patents and particularly theaforementioned U". S. Patents Nos;

2,575,558 and 2,582,985.

TABLE II 5 in essence an oversimplifieation'.

I 0-O-C- -0R --[B],,R O-C- CG 0 R1[R],.-R10O-CG H: H H: Ha H: H: H H,

(in which the characters have their previous significance) Example -R 0-from HR OH -R- n 7: Remarks number B1 Hydroxy benzene ..3 CH: 1 0,1,2Phenol known as bis-phenol A. Low polymeric mixture about as or morewhere n=0, remainder largely where I n =1, some where n"=2. CH:

B2 do OH: 1 0,1,2 Phenol known as bis-phenol B". see not 1 1 regarding131 above.

B3 Orthobutylphenol; CH3 1 0,1,2 Even though in is preferably 0, yet theusual reaction product might well con- .4 tain materials where n is 1,or to a lesser degree 2. O

B4 Orthoemylphenol IE: 1 0,1,2 Do.

I 1 CH:

B5; Orthooetylph'enolL (EH; 1' 0,1,2 Do.

B6 Orthonouylphenol H1 11 0,1,2 no.

B7 Orthododecylphenol CH: 1 0,1,2 Do.

B84... Metacresol OH; 1 0,1,2 See'prior note. This phenol used asinitial material is known as bis-phenol -.C-- C. For othersuitablebis-phenols see U. S. Patent 2,564,191; CH;

7 B9 -.do CH: 1 0,1,2 See prior note.

B10 Dibutyl (orthoqoaralphenol; I5 1 0,1,2 Do.

B11 Dlamyl (ortho-para) phenol. 1g 1 0,1,2 Do.

B12 Dioctyl (ortho-para) phenol. 1g 1 i 0, 1,2 Do.

B13 Dinonyl (ortho-para) phenol. 1 0,1,2 Do.

B144".-. Diamyl (ortho-para) phenol. g 1 0,1,2 Do.

I CH3: E

B15 "do H 1 0,1,2 Do;-

B16 Hydroxy benzene 1 0,1,2 Do.

,TABLE :1 Continued Example -R from HRIOH -R n n Remarks number I B17Diamyl phenol (ortho-para). -ss- 1 0,1,2 See prior notes.

B18 do -S- 1 .0,1,2 Do.

1319 Dlbutyl phenol (ortho-para). 1g 1g 1 0,1,2 Do.-

B20 do H H 1 0,1,2 Do."

B21 DinonylphenoMortho-para). H 132 1 0,1,2 Do.

B22 Hydroxy benzene O 1 0,1,2 Do.

B23 do None 0 0,1,2 Do.

B24 Ortho-lsopropyl phenol CH; 1 0,1,2 See prlornote. (Asto preparationof 4,4-

7 'lsopropylldene bis-(2-lsopropylphenol) C see U. 8. Patent No.2,482,748, dated .1 Sept. 27, 1949, to Dietzler.) CH3 I B25 Para-octylphenol CH:SOH, 1 0,1,2 See prior note. (As to preparation of the phenolsulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeskaet al.)

B26 Hydroxybenzene OH: 1 0,1,2 .See prior note. (As to preparation atthe l phenol sulfide see U. S. Patent No. C- 2,526,545.)

iii: 415K;

Subdivision C The prior examples have been limited largely to those inwhich there is no divalent linking radical, as in the case of diphenylcompounds, or where'the linking radical is derived from a ketone oraldehyde, particularly a ketone. Needless to say, thesame procedure isemployed in converting diphenyl into a diglicidyl ether regardless ofthe nature of thebond between the'two phenolic nuclei. For purpose ofillustration attention is directed to numerous other diphenols which canbe readily converted to a suitable polyepoxide, and particularlydiepoxide, reactant. As previously pointed out the initial phenol may besubstituted, and the substituent group in turn may be a cyclic groupsuch as the phenyl group or cyclohexyl groupas in the instance ofcyclohexylphenol or phenylphenol. Such substituents are usually in theortho position and may be illustrated by a phenol of the followingcomposition:

Similar phenols which are monofunctional, for instance, paraphenylphenol or paracyclohexyl phenol with an additional substituent in theortho position, may be em-' ployed in reactions previously referred to,for instance, with formaldehyde or sulfur chlorides to give comparablephenolic compounds having 2 hydroxyls and suitable for subsequentreaction with epichlorohydrin, etc! Other samples include:

| n 0 R1 (IE. R to wherein R is a substituent selected from the classconsisting of secondary butyl and tertiary butyl groups and R is asubstituent selected from the class consisting of alkyl, cycloalkyl,aryl, aralkyl, and alkaryl groups, and wherein said alkyl group containsat least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. See U. S. Patent No.2,504,064.

Colin C011" HO OH See U. S. Patent No. 2,285,563.

H OH; H CH: omit- 0H; d E

H0 0 OH in. Hg (IIH:

J7H-CH2 C \CH1 om-o,

See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxy-alkylradicals containing from 1 to 5 carbon atoms, inclusive, and aryl andchloraryl radicals of the benzene series. See U. S. Patent No.2,526,545.

OH OH Ha Ha wherein R is a substituent selected from the classconsisting of secondary butyl and tertiary butyl groups and R is asubstituent selected from the class consisting of alkyl, cycloalkyl,aryl, aralkyl, and alkaryl groups. See U. S.'Patent No. 2,515,906.

See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

(IJaHn C5 u See U. S. Patent No. 2,331,448.

As to the descriptions of various suitable phenol sulfides, reference ismade to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719,2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or someother aldehyde, particularly compounds such as H n o Alkyl R Alkyl Alkyl5 Alkyl 14 mula represents the various dicresol sulfides of thisinvention:

CH 0 H; OH

in which R and R are alkyl groups, the sum of whose carbon atoms equals6 to about 20, and R and R each preferably contain 3 to about 10 carbonatoms, and x is l to 4. The term sulfides as used in this text,therefore, includes mouosulfide, disulfide, and polysulfides.

PART 4 This part is concerned with the preparation of phenolaldehyderesins of the kind described in detail in U. S. Patent No. 2,499,370,dated March 7, 1950, to DeGroote and Keiser, With the followingqualifications: said aforementioned patent is limited to resins obtainedfrom difunctional phenols having 4 to 12 carbon atoms in the substituenthydrocarbon radical. For the present purpose the substituent may have asmany as 18 carbon atoms, as in the case of resins prepared fromtetradecylphenol, substantially paratetradecylphenol, commerciallyavailable. Similarly, resins can be prepared from hexadecylphenol oroctadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, refer once is made also tothe following U. S. Patents: Nos. 2,499,365; 2,499,366; and 2,499,367,all dated March 7, 1950, to De Groote and Keiser. These patents, alongwith the other two previously mentioned patents, described phenolicresins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are mostsatisfactory, with the additional C carbon atom also being verysatisfactory. The increased cost of the C and C carbon atom phenolrenders these raw materials of less importance, at least at the presenttime.

Patent 2,499,370 describes in detail methods of preparing resins usefulas intermediates for preparing the products of the present application,and reference is made to that patent for such detailed description andto Examples 1a through 103a of that patent for examples of suitableresins.

As previously noted, the hydrocarbon substituent in the phenol may haveas many as 18 carbon atoms, as illustrated by tetradecylphenol,hexadecylphenol and octadecylphenol, reference in each instance being tothe difunctional phenol, such as the orthoor para-substituted phenol ora mixture of the same. Such resins are described also in issued patents,for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to DeGroote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in anover-simplified form which has appeared from time to time in theliterature, and particularly in the patent literature, for instance, ithas been stated that the composition is approximated in an idealizedform by the formula OH on on H rt] 0 o HUH R R n R In the above formulan represents a small whole number varying from 1 to 6, 7 or 8, or more,up to probably 10 or 12 units, particularly when the resin is subjectedto heating under a vaccum as described in the literature. A limitedsub-genus is in the instance of low molecular weight polymers where thetotal number of phenol nuclei varies from 3 to 6, i. e., n varies from 1to 4; R represents an aliphatic hydrocarbon substituent, generally analkyl radical having from 4 to 14 carbon atoms, such as butyl, amyl,hexyl, decyl or dodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having 8 carbon atoms or less.

. In the above formula the aldehyde employed in the resin manufacture isformaldehyde. Actually, some other aldehyde such as acetaldehyde,propionaldehyde, or butyraldehyde may be used. The resin unit can beexemplified thus:

in which R' is the divalent radical obtained from the particularaldehyde employed to form the resin.

As previously stated, the preparation of resins, the kind hereinemployed as reactants, is well known. See U. S. Patent No. 2,499,368,dated March 7, 1950, to De Groote and Keiser. Resins can be made usingan acid catalyst or basic catalyst or a catalyst showing neither acidnor basic properties in the ordinary sense or without any catalyst atall. It is preferable that the resins employed be substantially neutral.In other Words, if prepared by using a strong acid as a catalyst, suchstrong acid should be neutralized. Similarly, if a strong base is usedas a catalyst it is preferable that the base be neutralized although wehave found that sometimes the reaction described proceeded more rapidlyin the presence of a small amount of a free base. The amount may be assmall as a 200th of a percent and as much as a few 100th of a percent.Sometimes moderate increase in caustic soda and caustic potash may beused. However, the most desirable procedure in practically every case isto have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. itis usually a mixture, for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n, as forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purpose of convenience suitable reins arecharacterized in the following table:

TABLE III M01. wt Ex- Position R of resin ample R 01 R derived nmolecule number from (based on n+2) Phenyl Para.-. 3. 5 992. 5

Tertiary butyl d0.... 3. 5 882.5 Secondary butyl. Ortho... 3. 5 882. 5Cyclo-hexyl Para-.. 3. 5 1, 025.5 Tertiary amyl- .do 3. 5 959. 5 Mixedsecondary Ortlio... 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 8.05. 5

s. 5 1, 03a. 3. 5 1, 190. a. 5 1, 267. 3. 5 1, 344. 3. 5 1,498. 3. 5945.

3. 5 1, 148. N onyl 3. 5 1, 456. Tertiary buty 3. 5 1,008.

Tertiary amyL. 3. 5 1, 085. Nonyl 3. 5 1, 393. Tertiary butyl 4. 2 996.

dehyde.

mmcn more: Lumen Ouncnmmm TABLE III-Oontlnued R!!! derived n fromPosition of R Parent- Tertiary amyl Nonyl 25a Tertiary butyl Tertiaryamyl. N onyl Tertiary amyl. gyalo-haxyl- PART 5 There have been issued asubstantial number of patents which give detailed description of thepreparation of oxyalkylated derivatives of resins of the kind previouslydescribed. For example, see U. S. Patents 2,499,365; 2,499,366;2,499,367; 2,499,368; and 2,499,370, all dated March 7, 1950 to DeGroote and Keiser.

More specifically, a number of other patents have appeared in whichtheoxyethylation step is given with considerable detail. See, forexample, U. S. Patents 2,581,376; 2,581,377; 2,581,378; 2,581,379;2,581,380, and 2,581,381, all dated January 8, 1952 to De Groote andKeiser. As to further examples, see U. S. Patent 2,602,052 dated July 1,1952 to De Groote.

The oxypropylation or, for that matter, the treatment of resins withbutylene oxide, glycide, or methylglycide, has been described in thefirst of the series in the above mentioned patents, i. e., those issuingin 1950.

Reference is made to U. S. Patent, 2,557,081 dated June 19, 1951 to DeGroote and Keiser. This particular patent describes in considerabledetail resins which are first treated with propylene oxide and then withethylene oxide or with. ethylene oxide and then propylene oxide or withboth oxides simultaneously.

In order to avoid an extensive repetition of what is already describedin detail in the patent literature, we are referring to the tablesbeginning in column 21 of U. S. Patent 2,581,376 and extending throughcolumn 36. We have simply numbered these products beginning with lb,allotting, of course, five numbers to each table beginning with thefirst table. For convenience these sixteen tables are summarized in thefollowing table:

TABLE IV 801- Ethyl- Ex. Phenol Aldehyde vent. Resin, ene No. lbs. lbs.oxide,

lbs.

1b Para-tertiary amyL. Formaldehyde 14. 25 15.75 4.00 25.... do .do10.90 12.10 15.25 7.13 7. 93 19. 69

TABLE IV Continued Sol- Ethyl- Ex. Phenol Aldehyde vent, Resin, one lbs.lbs. oxide, lbs.

216... Paaragseleondary Formaldehyde 14.45 15.65 4. 25

8.48 9.17 16.00 4.82 5.18 14.25 3.85 4.15 17.00 2.65 2. 85 15.45 12. 6017. 20 2. 75 8.55 11.50 9.30 3. 77 5.08 13.10 3.77 5.08 13.10 do 2.102.83 9.12 Para-tertiary amy1. 11.20 18.00 3. 50 do 8.45 13. 60 12. 654.50 8. 14.50 3.42 5. 48 15.10 2.05 3. 65 13.35 10. 25 17. 75 2. 50 7.6013.15 9.35 4.22 6.98 10.00 3.76 6.24 13.25 2.40 4.15 11.70 12. 18. 60 3.00 9. 25 14.25 11.00 6. 72 10. 32 14. 91 5. 52 8.52 19. 81 1.75 2.708.40 13.90 16. 70 3.00 10. 35 12.45 12.20 8.90 .10. 70 19. 00 5.20 6.2616. 64 3.60 4.32 15.68 10.85 20. 75 3. 00

Norm-For ease of comparison blanks appear in the above tables whereblanks appear in previously mentioned tables in U. S. Patent 2,581,376.

Oxypropylated derivatives comparable to 117 through 805 as describedabove can readily be obtained by substituting a molar equivalent amountof propylene oxide, i. e., 56 lbs. of propylene oxide, for example, foreach 44 lbs. of ethylene oxide. We have prepared such a similar seriesbut for sake of brevity only a few will be included for purposes ofillustration.

18 As an illustration of oxypropylated resins involving the use of bothethylene and propylene oxide, reference is made to the aforementioned U.S. Patent 2,557,081, dated June 19, 1951 to De Groote and Kaiser. Thelast table in column 28 of said patent describes in detail thepreparation of a series of oxyalkylated resins in which both propyleneand ethylene oxide are employed. Simply by way of illustration 2 seriesof 27 compounds are included, the descriptions of which apear in detailin said aforementioned U. S. Patent 2,577,081 to De Groote and Keiser.

TABLE VI See U. S. Pat. 2,557,081

Ethyl- Pro- Wt. Flk. Ex. Ex. Point Resin used Resin, ene pylene ofcaustic No. No. on lbs. oxide, oxide, xysoda,

in graph lbs. lbs. lene ounces above on patent above pat.

1d,. A 1 Tart. amyl 6 3 1 1O 1 phenol 2a-- 13--.. 5 5 4 1 10 1 32.-0.--- s 3 e 1 10 1 42.. D. 2 1 21.5 2.5 25 2 511.. 9 1 15 9 25 2 6d..-

e 1 10 15 25 2 7a.- G a 1 2.5 21.5 25 2 8d 11.... 7 5 1 4 10 1 911-- 4 61 a 10 1 10d. 14---- 1 6 a 1 10 1 11a. 3.... 5 5 4 1 10 1 12d. 0.-.. s 3e 1 10 1 132. D. 2 1 21.5 2.5 25 2 14d. 9 1 15 9 25 2 15d. 6 1 10 14 252 16d. (1%.... 3 1 2.5 21.5 25 2 17d. H.. 7 5 1 4 10 1 18d- 20 11..-. a5 4 1 10 1 21 0.... a 3 6 1 10 1 221 D 2 1 21.5 2.5 25 2 23d. 9 1 15 925 2 2411 F--- e 1 10 -14 25 2 251 (1..-- 3 1 2.5 21.5 25 2 26d. 13...-7 5 1 4 10 1 27d. 4 e 1 3 10 1 Note the first series of nine compounds,1d through 9d, were prepared with a propylene oxide first and thenethylene oxide. The second 9, 10d through 18d inelusive, were preparedusing ethylene oxide first and then propylene oxide, and the last 9, 19dthrough 270! were prepared by random oxyalkylation, i. e., using amixture of two oxides.

In the preparation of the resins our preference is to use hydrocarbonsubstituted phenols, particularly para-substituted, in which thesubstituted radical R contains 4 to 18 carbon atoms and particularly 4to 14 carbon atoms.

TABLE V Ex. Oxypro- Solvent, Resin, Propyl- No. pylated Phenol Aldehydelbs. lbs. ene oxide,

analog lbs.

Paratertiary amyl. Formaldehyde. 14. 25 15. 72 5. 10 do do 10.90 12.1019. 40 7. 13 7. 93 25. 30 3. 84 4. 25 23. 00 1. 80 2. 04 13. 00 13.3016. 90 3. 82

19 The amount of alkylene oxide introduced may be comparatively large incomparison to the initial resin. For instance, there may be as much as50 parts by weight of an oxide or mixed oxides used for each part byweight of resin employed.

It will be noted that the various resins referred to in theaforementioned U. S. Patent 2,499,370 are substantially the same type ofmaterials as referred to in Table I. For instance, resin 3:: of thetable is substantially the same as 2a of the patent; resin 20a of thetable is substantially the same as 34a of the patent; resin 38:; of thetable is the same as 3a of the patent.

In reaction with polyepoxides, and particularly diepoxides, a largenumber of the previously described oxyalkylated resins have beenemployed. For convenience, the following list is selected indicating thepreviously described compounds and their molecular weights. Such resinsare generally employed at a 50% solution and the polyepoxide employed isa 50% solution, usually both reactants being dissolved in xylene andsur'licient sodium methylate added to act as a catalyst, for instance, 1to 2%.

TABLE VII Ex. No.: M01. wt. Ex. No.: M01. wt 1b 1,202 30 4,019 2b 2,16940 6,139 3b 3,339 50 7,079 4b 4,609 la! -n 1,697 5b 5,749 2d 1,918 6b1,509 3d 3,189 75 2,466 451 23,959 8b 3,657 561 23,959 9b 5,867 64124,909 10b 6,087 7d 23,959 10 1,270 8d 1,918 26 2,494 9d 1,697

PART 6 As previously pointed out, having the two types of reactantsrequired for intermediate manufacture, i. e., the oxyalkylatedphenol-aldehyde resins and the diglycidyl ethers or their equivalent,one can then proceed to combine 2 moles of the oxyalkylatedphenol-aldehyde resin with one mole of the ether. The reaction isessentially an oxyalkylation reaction and thus may be considered asmerely a continuance of the previous oxyalkylation reaction. Theprevious oxyalkylation reaction involved a monoepoxide as differentiatedfrom a polyepoxide and particularly a diepoxide. The reactions takeplace in substantially the same way, i. e., by the opportunity to reactat somewhere above the boiling point of water and belowthe point ofdecomposition, for example,

130-185 C. in the presence of a small amount of alkaline catalyst. Sincethe polyepoxide is non-volatile as compared, for example, with ethyleneoxide, the reaction is comparatively simple. Purely from a mechanicalstandpoint it is a matter of convenience to conduct both classes ofreactions in the same equipment. In other words, after thephenol-aldehyde resin has been reacted with ethylene oxide, propyleneoxide or the like, it is subsequently reacted with a polyepoxide. Thepolyepoxide reaction can be conducted in an ordinary reaction vesselsuch as the usual glass laboratory equipment. This is particularly trueof the kind used for resin manufacture as described in a number ofpatents, as for example, U. S. Patent No. 2,499,365. One can use avariety of catalysts in connection with the polyepoxide of the sameclass employed with monoepoxide. in fact, the reaction will go at anextremely slow rate without any catalyst at all. The usual catalystsinclude alkaline materials such as caustic soda, caustic potash, sodiummethylate, etc. Other catalysts may be acidic in nature and are of thekind characterized by iron and tin chlorides.

approximately one-half hour.

more exactly, 1.1 grams.

Furthermore, insoluble catalysts such as clays or specially preparedmineral catalysts have been used. For practical purposes, it is best touse the same catalyst as is used in the initial oxyalkylation step andin many cases there is sufiicient residual catalyst to serve for thereaction involving the second oxyalkylation step, i. e., thepolyepoxide. For this reason, we have preferred to use a small amount offinely divided caustic soda or sodium methylate as the initial catalystand also the catalyst in the second stage. The amount generally employedis 1, 2, or 3% of these alkaline catalysts.

Actually, the reactions of polyepoxides with various resin materialshave been thoroughly described in the literature and the procedure is,for all purposes, the same as with glycide which has been describedpreviously.

It goes without saying that the reaction involving the polyepoxide canbe conducted in the same manner as the monoepoxide as far as thepresence ofan inert solvent is concerned, i. e., one that is notoxyalkylationsusceptible. Generally speaking, this is most convenientlyin aromatic solvent such as xylene or a higher boiling coal tar solvent,or else a similar high boiling aromatic solvent obtained from petroleum.One can employ an oxygenated solvent such as the diethylether ofethylene glycol, or the diethylether of propylene glycol, or similarethers, either alone or in combination with a hydrocarbon solvent. Thesolvent so selected should be one which, of course, is suitable in theoxyalkylation step involving the monoepoxide described subsequently. Thesolvent selected may depend on the ability to remove it by subsequentdistillation if required. Here again it has been our preference to havea solvent present in the oxyalkylation involving the initial stage andpermitting the solvent to remain. The amount of solvent may beinsignificant, depending whether or not exhaustive oxyalkylation isemployed. However, since the oxyalkylated phenol-aldehyde resins arealmost invariably liquids there is no need for the presence of a solventas when oxyalkylation involves a solid which may be rather high melting.Thus, it is immaterial whether there is a solvent present or not :and itis immaterial whether solvent was added in the first stage ofoxyalkylation or not, and also it is immaterial whether there wassolvent present in the second stage of oxyalkylation or not. Theadvantage of the presence of solvent is that sometimes it is aconvenient way of controlling the reaction temperature and thus in thesubsequent examples we have added sufficient xylene so as to produce amixture which boils somewhere in the neighborhood of to C. and removesxylene so as to bring the boiling point of the mixture to about 140 C.during part of the reaction and subsequently removing more xylene sothat the mixture refluxed at somewhere between to C. This was purely aconvenience and need not be employed unless desired.

Example la The oxyalkylated resin employed was the one previouslyidentified as 2b, having a molecular weight of 2169; the amount employedwas 217 grams. The resin was dissolved in approximately an equal weightof xylene. The mixture was heated to just short of the boiling point ofwater, i. e., a little below 100 C. Approximately one-half percent ofsodium methylate was added, or, The stirring was continued until therewas a solution or distribution of the catalyst. The mixture was heatedto a little past 100 C. and left at this temperature while 17 grams ofthe diepoxide (previously identified as 3A), dissolved in an equalweight of xylene, were added. After the diepoxide was added thetemperature was permitted to rise to approximately 107 C. The timerequired to add the diepoxide was The temperature rose in this period toabout 125 C. The temperature rise was Controlled by allowing the xyleneto reflux over and to 21 separate out the xylene by a phase separatingtrap. In any event, the temperature was raised shortly to 138- 140 C.and allowed to reflux :at this temperature for peroxides or by othersuitable means and the diglycidyl ethers may be indicated thus H H H Halmost three hours. Tests indicated that the reactlon HO-OC-CH wascomplete at the end of this time; in fact, it probably was complete at aconsiderably earlier stage. The xylene which had been separated out wasreturned to the CH1 mixture so that the reaction mass at the end of thepro- I H cedure represented about reaction product and 50% HOWCPCWCHsolvent. The procedure employed, is, of course, simple i0 0 0 m hght ofWhat has been Sald Prevlously It in some lnstances the compounds areessentially derivaresponds to the usual procedure employed 1n connectionp uves of ethenzed epichlorohydrm or methyl ep1chlorowlth anoxyalkylatmg agent such as glyc1de, 1. e., a nonh ydrin. Needless tosay, such compounds can be derived volatile oxyalkylating agent. At theend of the reaction from 1 cerol monochlomh drin b etherization riot toperiod the mass obtained was a dark, viscous mixture. 5 gy y P It couldbe bleached of course by use of charcoal filternng example ls ustrated mthe prevlously mentioned Italian Patent No. 400,973: mg earths, or thelike.

Various examples obtained in substantially the same CE2;OHOH:O-OHr-C\1/-QHI manner as employed are described in the following table: 0 0

TABLE VIII Ex. Oxyalkyl- Amt, Diepox- Amt, Catalyst Xylene, Molar Timeoi Max. No. ated gms. ide gms. (N20011:), gms. ratio reaction, temp.,Color and physical state resin used grams s. 0.

217 3A 17 1.1 234 2:1 3 Dark viscous mass. 250 3A 17 2.4 477 2:1 4 D0.247 3A 17 1.3 254 2:1 3 Do. 509 3A 17 3.1 526 2:1 4 148 Do. 249 3A 171.3 255 2:1 2.5 150 Do. 402 8A 17 2.0 419 2:1 4 146 Do. 708 3A 17 3.5725 2:1 5 152 D0. 192 3A 17 1.0 200 2:1 2.5 142 Do. 319 3A 17 1.0 3362:1 3 147 Do. 249 311 17 1.2 250.7 2:1 3 Do. 217 B1 27.5 1.2 244.5 2:13.5 145 Do. 450 B1 27.5 2.4 487.5 2:1 4 150 Do. 247 B1 27.5 1.3 274.52:1 4 152 Do. 509 B1 27.5 3.1 535.5 2:1 5 158 Do. 249 B1 27.5 1.3 275.52:1 4 145 Do. 402 B1 27.5 1.2 429.5 2:1 5 150 Do. 708 B1 27.5 2.6 735.52:1 5 152 Do. 192 B1 27.5 1.0 219.5 2:1 3.5 148 Do. 319 B1 27.5 1.7345.5 2:1 4 150 Do. 249 B1 27.5 1.2 251.8 2:1 3 152 Do.

TABLE IX Another type of diepoxide is diisobutenyl dioxide as describedin aforementioned U. S. Patent No. 2,070,990, P ob ble oxyalkyb f gAmount Amount 4 dated February 16, 1937, to Groll, and 1s of thefollowing Ex. No. ated resin weight of product, solvent, 0 form l usedreaedtiot grams grams pro uc H C O-CH CHr-CIl CH 4, 680 4, 680 2, 340 9,540 4, 770 2, 395 CH5 011: 5,280 5,280 2, 540 50 g: g; g; The diepoxidespreviously descnbed may be indicated by 8; 320 8,370 4,180 the followingformula: 14, 500 7, 250 3, 025

4, 4, 2,105 11 R R H .953 2 52 41890 41990 21445 55 0, 750 4, 880 4:013: $38 31 511 92 in which R represents a hydrogen atom or methyl 3 238Z: radical and R" represents the divalent radical uniting the 141710 3 3two terminal epoxide groups, and n is the numeral 0 or g, 4, g 60 1. Aspreviously pointed out, in the case of the butadiene 50:32) 5 40 2:525derivative, 71 is 0. In the case of diisobutenyl dioxide R is CH CH andn is 1. In another example previous- ART 7 1y referred to R" is CH OCHand n is 1. P However, for practical purposes the only diepoxideReference is made to various patents to illustrate the 05 available inquantities other than laboratory quantities is manufacture of thenon-aryl hydrophile polyepoxides and a derivative of glycerol orepichlorohydrin. This particuparticularly diepoxides employed asreactants in the inlar diepoxide is obtained from diglycerol whlch islargely stant invention. More specifically, such patents are the acyclicdiglycerol, and epichlorohydrin or equrvalent following: Italian PatentNo. 400,973, dated August 8, thereof, in that the epichlorohydrin itselfmay supply the 1941; British Patent No. 518,057, dated December 10, 70glycerol or diglycerol radical in addition to the epoxy 1938; U. S.Patent No. 2,070,990, dated February 16, rings. As has been suggestedpreviously, instead of start- 1937 to Groll et al.; and U. S. Patent No.2,581,464, ing with glycerol or a glycerol derivative, one could startdated January 8, 1952, to Zech. The simplest diepoxide with any one of anumber of glycols or polyglycols and is probably the one derived from1,3-butadiene or isoit is more convenient to include as part of theternunal prene. Such derivatives are obtained by the use of 75 oxiranering radical the oxygen atom that was denved 23. from epichlorohydrinor, as might.be1the case,,methyl epichlorohydrin. So presented theformula becomes:

In the above formula R is selected from groups such as the following:

CaHEOCiHa" a a( s a( aH(OH) It is to be notedthat in the above epoxidesthere is a complete absence of (a) aryl radicals and (b) radicals inwhich 5 or more carbon atoms are united in a single uninterrupted singlegroup. R is inherently hydrophile in character as indicated by the factthat it is specified that the precursory diol or polyol HOROH must bewatersoluble in substantially all proportions, i. e., Water miscible.

Stated another way, what is said previously means that a polyepoxidesuch as is derived actually or theoretically, or at least derivable,from the diol HOROH, in which the oxygen-linked hydrogen atoms werereplaced by Thus, R(OH),,, where n represents a small whole number whichis 2 or more, must be water-soluble. Such limitation excludespolyepoxides it actually derived, or theoretically derivedat least, fromwater-insoluble diols or water-insoluble triolsor higher polyols.Suitable polyols may contain as many as 12 to carbon atoms orthereabouts.

Referring to a compound of the type above in the formula in which R is CH (OH), it is obvious that reaction with another mole of epichlorohydrinwith appropriate ring closure would produce a triepoxide, or, similarly,if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide.Actually, such procedure generally yields triepoxides, or mixtureswithhigher epoxides and perhaps in other instancesmixtures in whichdiepoxides are also present. Our preference is to use the diepoxides.

Thereis-available commercially at least one diglycidyl etherfree fromaryl groups and also free from any radical having 5 or more carbon atomsin an uninterrupted chain. This particular diglycidyl ether is obtainedby the use of epichlorohydrin in such a manner that approximately.4moles of epichlorohydrin yield one mole of the diglycidylether, or,stated another way, it can be consid'ered as being formed from one moleof diglycerol and 2 moles of epichlorohydrin so as to give theappropriate diepoxide. The molecular weight is approximately 370 and thenumber of epoxide groups per molecule are approximately 2. For: thisreason in the first of a series of subsequent examples this particulardiglycidyl other is used,.although obviously any of the otherspreviously described would... be justvas suitable. For convenience, thisdepoxide will be referred to as diglycidyl ether A.

Such. material corresponds, inat-generaLwaywto thvprevi v 1 ous.formula;

Using laboratory procedurewe'have: reacted diethyl eneglycol withepichlorohydrin and subsequently: with alkali was to produceaproductwhich, on-examination,

corresponded approximately to the following compound:

The molecular-weight of the product was assumed to be 230 and'theproduct was available in laboratory quantities only. For this reason,the subsequent table referring to the use of this particular diepoxide,which will be referred to as diglycidyl ether'B is in grams instead ofpounds.

Probably the simplest terminology for these polyepoxides, andparticularly diepoxides, to differentiate from comparable arylcompounds, is to use the terminology epoxyalkanes and, moreparticularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is thatthe majority ofthese compounds represent types in which a carbon atomchain is interrupted by an oxygen atom, and thus, they are not strictlyalkanederivatives. Furthermore, they may be hydroxylated or represent abeterocyclic ring. The principal class properly may be re-' ferred to aspolyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a'heterocyclic ring having, forexample, 3 carbon atoms and 2 oxygen atoms, are obtainable by theconventional reaction of combining erythritol with carbonyl compound,such as formaldehyde or acetone so as'to form the 5 membered ring,followed by conversion of the terminal hydroxyl groups into epoxyradicals. See also Canadian Patent No. 672,935.

PART 8 As pointed out previously, the reaction described in Part 6,preceding, resulted in an intermediate which was described thus:(AB--A). The reaction described in the instant part has been indicatedthus:

The manufacturing procedure is, of course, merely a continuation of whathas been described previously in Part 6 and it is simply a switch fromthe one type of polyepoxide to the other. Of course, after thehydrophobe polyepoxide is added, suiiicient time should pass to insurecompleteness of reaction before adding the hydrophile type. For purposeof illustration, however, the following examples are included:

Example 1g The polyepoxide derived intermediate is Example le,previously described in Table VIII. This was obtained by use of ahydrophobe type polyepoxide. 234 grams were employed. These were reactedwith 9.3 grams-of cliepoxide A, previously described. The amount ofcatalyst present was 2.4 grams of powdered sodium methylate. The amountof xylene was 243 grams. The molal ratio was 2 moles of .thepolyepoxide-derived intermediate to one mole of diepoxide A. Thecatalyst, the solvent, and the intermediate were all mixed together andstirred. The diepoxide was then added slowly over a period of less thana half-hour. The temperature was raised to l4 l C. and held at thistemperature for about 2 hours. The product obtained was a dark viscousmass when the solvent was evaporated. On completion of the reactionenough acetic acid was added to neutralize the catalyst.

in a second series of derivatives, hydrophile diepoxide B was employed.Both have been described previously in Part 7, preceding.

The data are summarized in hereto appended Tables X and XI.

It is not necessary to point out that after reaction with a reactant ofthe kind described which introduces a basic TableX Polyepoxide Dl-Catalyst Time of Ex. derived epoxide Amt, (N aOGHa), Xylene, Molarreaction, Max. Color and physlcalSt. No. inter- Amt, used gins. gins.'gms. ratio hrs. temp,

mediate grns. O. product 234 A 9. 3 2. 4 243 2:1 2 140 Dk. viscous mass.477 A 9. s 4. s 486 2:1 2 142 Do. 254 A 9. a 2. 7 273 2:1 2 145 Do. 250A 3. 7 2. 5 254 2: 1 2 140 Do. 255 A 9. 3 2. 7 275 2: 1 2 140 Do. 419 A9. 3 4. 2 425 2:1 2 145 Do. 290 A a. 7 2. 9 294 2: 1 2 145 Do. 209 A 9.3 2. 1 21s 2: 1 2 140 Do. 335 A 9. a a. 4 243 2: 1 2 147 Do. 501 A 1. 95. 505 2: 1 2 150 Do. 234 B 5.5 2.4 240 2:1 2 150 Do. 477 B 5. 5 4. a283 2:1 2 145 Do. 254 B 5. 5 2. 7 270 2: 1 2 147 Do. 250 B 2. 2 2. 5 2522:1 2 145 Do. 255 B 5.5 2.7 272 2:1 2 145 Do. 419 B 5. 5 4. 2 425 2:1 2140 Do. 290 B 2. 2 2. 9 292 2: 1 2 145 Do. 209 B 5. 5 2.1 2. 5 2:1 2 145Do. 335 B 5. 5 3. 4 342 2:1 2 150 Do. 501 B 1. 1 5. 0 502 2: 1 2 145 D0.

Table XI nitrogen atom that the resultant product can be employed forthe resolution of emulsions of the water-in-oil type 0 1k 1 rn ibat ie At x A t f as described in Part 7, preceding, and also for other purxyaymo ecu ar moun o moun o Ex. No. ated resin weight of product, solvent,Poses desfmbed hemmafter' used re aoitioltll gr grams Referring now tothe use of the products: obtained by reaction with a polyepoxide andcertain specified oxyalkylated products obtained in the manner describedin 9,730 4,855 2,432 19,450 3,890 1,945 Part 6 preceding, 1t is to benoted that in add1t1on to gig or their use in the resolution ofpetroleum emulsions they 111010 51505 21752 may be used as emulsifyingagents for oils, fats, and Waxes; as ingredients in insecticidecompositions; or as 8:730 41355 2:182 detergents and wetting agents inthe laundering, scourgfi ing, dyeing, tanning and mordanting industries.They 101000 51000 2, 590 40 may also be used for preparing boring ormetal-cutting 358 g: 1 oils and cattle dips, as metal picklinginhibitors, and for 25,680 5,136 2, 568 pharmaceutical purposes. iljgg5:258 Hi3 Not only do these oxyalkylated derivatives have utility 29,640 2, 3% as suchbut they can serve as initial materials for more ,iggg2:816 1:408 complicated reactions of the kind ordinarily requiring100,960 ,0 2,019 a hydroxyl radical. This includes esterification,etherization, etc.

PART 9 As to the use of conventional demulsifying agents, reference ismade to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part 3. Everything that appears therein applied withequal force and effect to the instant process, noting only that wherereference is made to Example 13b in said text beginning in column 15 andending in column 18, reference should be to Example 1g. hereindescribed.

PART 10 wherein R and R" are alkyl groups.

The oxyalkylated derivatives may be used as valuable additives tolubricating oils, both those derived from petroleum and syntheticlubricating oils. Also, they can be used as additives to hydraulic brakefluids of the aqueous and non-aqueous types. They may be used inconnection with other processes where they are in jected into an oil orgas well for purpose of removing a mud sheath, increasing the ultimateflow of fluid from the surrounding strata, and particularly in secondaryre covery operations using aqueous flood waters. These dorivatives alsoare suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initialresin, the particular monoepoxide selected, and the ratio of monoepoxideto resin, together with the particular polyepoxide employed, result in avariety of materials which are useful as wetting agents or surfacetension reducing agents; as detergents, emulsifiers or dispersingagents; as additives for lubricants, both of the natural petroleum typeand the synthetic type; as additives in the flotation of ores, and attimes as aids in chemical reactions in so far that demulsification isproduced between the insoluble reactants. Furthermore, such products canbe used for a variety of other purposes, including use as corrosioninhibitors, defoamers, asphalt additives, and at times even in theresolution of oil-inwater emulsions. They serve at times as mutualsolvents promoting a homogeneous system from two otherwise insolublephases.

Havingtthus 'describedour invention, what we claim new and desire tosecure by Letters Patent is:

1. A two-step manufacturing method, the first step involving anintermediate (ABA) which, in turn, represents the reaction products of(A) an oxyalkylated phenolaldehyde resin containing, a plurality ofactive hydrogen atoms, and (B) a phenolic polyepoxide containing atleast two 1,2-epoxy rings free from reactive functional groups otherthan 1,2-epoxy and hydroxyl groups, and cogenerically associatedcompounds formed in the preparation of said polyepoxides; said epoxidesbeing monomers and low molal polymers not exceeding the tetrarners; saidepoxides being selected from the class consisting of (a) compounds wherethe phenolic nuclei are directly joined without an intervening bridgeradical, and (b) compounds containing a radical in which two phenolicnuclei are joined by a divalent radical selected from the classconsisting of ketone residues formed by the elimination of the ketonicoxygen atom, andaldehyde residues obtained by the elimination of thealdehyde. oxygen atom, the divalent radical the divalent radical, thedivalent sulfone radical, and the divalent monosulfide radical -S, thedivalent radical CH SCH and the divalent disulfide radical -SS-; saidphenolic portion of the diepoxide being. obtained from a phenol of thestructurein which R, R", and R represent a member of the classconsisting of hydrogen and hydrocarbon substituents of the aromaticnucleus, said substituent member having not over 18 carbon atoms; saidoxyalkylated phenol-aldehyde resins, reactant (A) being the products ofoxyalkylation of (an) an alpha-beta alkylene oxide having not more than4 carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide, and (bb) afusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in substantial absence oftrifunctional phenols; said phenol being of the formula in which R isselected from the group consisting of phenyl and saturated hydrocarbonradicals having not more than 24 carbon atoms and substituted in the2,4,6 position; said oxyalkylated resin being characterized by theintroduction into the resin molecule. of a plurality of divalentradicals having the formula (R O),,, in which R is a member selectedfrom the class consisting of ethylene radicals, propylene radicals,butylene radicals, hydroxypropylene radicals, and hydroxybntyleneradicals, and n is a numeral varying from 1 to 120; with the provisothat at least 2 moles of alkylene'oxide be introduced for each phenolicnucleus, and'tl'iat the resin by weight represent at least 2% of theoxyalkylated derivative; the ratio of reactant (A) to reactant (B) beingin the proportion of two moles of (A) to one mole of (B); with thefurther proviso that said reactive compounds (A) and (B) be members ofthe class consisting of non-thermosetting organic solvent-solubleliquids and solids melting below the point of pyrolysis; with the finalproviso that the re-- polyepoxide containing at least two 1,2-epoxyrings and having two terminal 1,2-epoxy rings obtained by replacement ofan oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol bythe radical said polyepoxides being free from reactive functional groupsother than 1,2-epoxy and hydroxyl groups and characterized by the factthat the divalent linkage uniting the terminal oxirane rings is freefrom any radical having more than 4 uninterrupted carbon atoms in asingle chain; said final product being a member of the class consistingof non-thermosetting organic solvent-soluble liquids and solids meltingbelow the point of pyrolysis with the final proviso that the reactionproduct be a member of the class of solvent-soluble liquids and solidsmelting below the point of pyrolysis; and said reaction between (ABA)and (C) being conducted below the pyrolytic point of the reactants andthe resultants of reaction.

2. The product obtained by the manufacturing procedure defined in claim1.

3. A two-step manufacturing method, the first step involving anintermediate (ABA) which, in turn, represents the reaction products of(A) an oxyalkylated phenolaldehyde resin containing a plurality ofactive hydrogen atoms, and (B) a member of the class consisting of (1)compounds of the following formula:

and (2) generically associated compounds formed in the preparation of(1) preceding, including monoepoxides; said oxyalklated phenol-aldehyderesins, reactant (A), beingthe products derived by oxyalklation of (aa)an alphabeta alkylene oxide having not more than 4 carbon atoms in whichR is selected from the group consisting of phenyl and saturatedhydrocarbon radicals, having not more than 24 carbon atoms andsubstituted in the 2,4,6 position; said oxyallrylated resin beingcharacterized by the introduction into the resin molecule of a pluralityof divalent radicals having the formula (R O),," in which R is a memberselected from the class consisting of ethylene radicals, propyleneradicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals,

29 and n" is a numeral varying from 1 to 120; with the proviso that atleast 2 moles of alkylene oxide be introduced for each phenolic nucleus,and that the resin by weight represent at least 2% of the oxyalkylatedderivative; the ratio of reactant (A) to reactant (B) being in theproportion of two moles of (A) to one mole of (B); with the furtherproviso that said reactive compounds (A) and (B) be members of the classconsisting of nonthermosetting organic solvent-soluble liquids andsolids melting below the point of pyrolysis; with the final proviso thatthe reaction product be a member of the class of solvent-soluble liquidsand solids melting below the point of pyrolysis; and said reactionbetween (A) and (B) being conducted below the pyrolytic point of thereactants and the resultants of reaction; said second step being thereaction product between 2 moles of the aforementioned intermediate(ABA) and one mole of (C) a non-aryl hydrophile polyepoxide containingat least two 1,2-epoxy rings and having two terminal 1,2-epoxy ringsobtained by replacement of an oxygen-linked hydro- 3% gen atom in awater-soluble polyhydric alcohol, by the radical said polyepoxides beingfree from reactive functional groups other than 1,2-epoxy and hydroxylgroups and characterized by the fact that the divalent linkage unitingthe terminal oxirane rings is free from any radical having more than 4uninterrupted carbon atoms in a single chain; said final product being amember of the class consisting of non-thermosetting organicsolvent-soluble liquids and solids melting below the point of pyrolysis;with the final proviso that the reaction product be a member of theclass of solvent-soluble liquids and solids melting below the point ofpyrolysis; and said reaction between (ABA) and (C) being conducted'belowthe pyrolytic point of the reactants and the resultants of reaction.

No references cited.

1. A TWO-STEP MANUFACTURING METHOD, THE FIRST STEP INVOLVING ANINTERMEDIATE (ABA) WHICH, IN TURN, REPRESENTS THE REACTION PRODUCTS OF(A) AN OXYALKYLATED PHENOLALDEHYDE RESIN CONTAINING A PLURALITY OFACTIVE HYDROGEN ATOMS, AND (B) A PHENOLIC POLYEPOXIDE CONTAINING ATLEAST TWO 1,2-EPOXY RINGS FREE FROM REACTIVE FUNCTIONAL GROUPS OTHERTHAN 1,2-EPOXY AND HYDROXYL GROUPS, AND COGENERICALLY ASSOCIATEDCOMPOUNDS FORMED IN THE PREPARATION OF SAID POLYEPOXIDES; SAID EPOXIDESBEING MONOMERS AND LOW MOLAL POLYMERS NOT EXCEEDING THE TETRAMERS; SAIDEXPOXIDES BEING SELECTED FROM THE CLASS CONSISTING OF (A) COMPOUNDSWHERE THE PHENOLIC NUCLEI ARE DIRECTLY JOINED WITHOUT AN INTERVENINGBRIDGE RADICAL, AND (B) COMPOUNDS CONTAINING A RADICAL IN WHICH TWOPHENOLIC NUCLEI ARE JOINED BY A DIVALENT RADICAL SELECTED FROM THE CLASSCONSISTING OF KETONE RESIDUES FORMED BY THE ELIMINATION OF THE KETONICOXYGEN ATOM, AND ALDEHYDE RESIDUES OBTAINED BY THE ELIMINATION OF THEALDEHYDE OXYGEN ATOM, THE DIVALENT RADICAL